Use of core-shell particles

ABSTRACT

The invention relates to the use of core/shell particles whose shell forms a matrix and whose core is essentially solid and has an essentially monodisperse size distribution and whose shell is bonded to the core via an interlayer and whose shell has thermoplastic properties for the production of mouldings having homogeneous, regularly arranged cavities, to a process for the production of mouldings having homogeneous, regularly arranged cavities, and to the corresponding mouldings.

The invention relates to the use of core/shell particles for the production of mouldings having homogeneous, regularly arranged cavities, to a process for the production of mouldings having homogeneous, regularly arranged cavities, and to the corresponding mouldings.

For the purposes of the present invention, mouldings having homogeneous, regularly arranged cavities are materials which have three-dimensional photonic structures. The term three-dimensional photonic structures is generally taken to mean systems which have a regular, three-dimensional modulation of the dielectric constants (and thus also of the refractive index). If the periodic modulation length corresponds approximately to the wavelength of (visible) light, the structure interacts with the light in the manner of a three-dimensional diffraction grating, which is evident from angle-dependent colour phenomena. An example of this is the naturally occurring precious stone opal, which consists of silicon dioxide spheres in spherical closest packing with air- or water-filled cavities in between. The inverse structure thereto is notionally formed by regular spherical cavities being arranged in closest packing in a solid material. An advantage of inverse structures of this type over the normal structures is the formation of photonic band gaps with much lower dielectric constant contrasts still (K. Busch et al. Phys. Rev. Letters E, 198, 50, 3896).

Three-dimensional inverse structures can be produced by template synthesis:

-   -   Monodisperse spheres are arranged in spherical closest packing         as structure-forming templates.     -   The cavities between the spheres are filled with a gaseous or         liquid precursor or a solution of a precursor utilising         capillary effects.     -   The precursor is converted (thermally) into the desired         material.     -   The templates are removed, leaving behind the inverse structure.

Many such processes are disclosed in the literature. For example, SiO₂ spheres can be arranged in closest packing and the cavities filled with tetraethyl orthotitanate-containing solutions. After a number of conditioning steps, the spheres are removed using HF in an etching process, leaving behind the inverse structure of titanium dioxide (V. Colvin et al. Adv. Mater. 2001, 13, 180).

De La Rue et al. (De La Rue et al. Synth. Metals, 2001, 116, 469) describe the production of inverse opals consisting of TiO₂ by the following method: a dispersion of 400 nm polystyrene spheres is dried on a filter paper under an IR lamp. The filter cake is washed by sucking through ethanol, transferred into a glove box and infiltrated with tetraethyl orthotitanate by means of a water-jet pump. The filter paper is carefully removed from the latex/ethoxide composite, and the composite is transferred into a tubular furnace. Calcination in a stream of air is carried out in the tubular furnace at 575° C. for 8 hours, causing the formation of titanium dioxide from the ethoxide and burning out the latex particles. An inverse opal structure of TiO₂ remains behind.

Martinelli et al. (M. Martinelli et al. Optical Mater. 2001, 17, 11) describe the production of inverse TiO₂ opals using 780 nm and 3190 nm polystyrene spheres. A regular arrangement in spherical closest packing is achieved by centrifuging the aqueous sphere dispersion at 700-1000 rpm for 24-48 hours followed by decantation and drying in air. The regularly arranged spheres are moistened with ethanol on a filter in a Buchner funnel and then provided dropwise with an ethanolic solution of tetraethyl orthotitanate. After the titanate solution has percolated in, the sample is dried in a vacuum desiccator for 4-12 hours. This filling procedure is repeated 4 to 5 times. The polystyrene spheres are subsequently burnt out at 600° C.-800° C. for 8-10 hours.

Stein et al. (A. Stein et al. Science, 1998, 281, 538) describe the synthesis of inverse TiO₂ opals starting from polystyrene spheres having a diameter of 470 nm as templates. These are produced in a 28-hour process, subjected to centrifugation and air-dried. The latex templates are then applied to a filter paper. Ethanol is sucked into the latex template via a Bochner funnel connected to a vacuum pump. Tetraethyl orthotitanate is then added dropwise with suction. After drying in a vacuum desiccator for 24 hours, the latices are burnt out at 575° C. for 12 hours in a stream of air.

Vos et al. (W. L. Vos et al. Science, 1998, 281, 802) produce inverse TiO₂ opals using polystyrene spheres having diameters of 180-1460 nm as template. In order to establish spherical closest packing of the spheres, a sedimentation technique is used supported by centrifugation over a period of up to 48 hours. After slow evacuation in order to dry the template structure, an ethanolic solution of tetra-n-propoxy orthotitanate is added to the latter in a glove box. After about 1 hour, the infiltrated material is brought into the air in order to allow the precursor to react to give TiO₂. This procedure is repeated eight times in order to ensure complete filling with TiO₂. The material is then calcined at 450° C.

The production of photonic structures from inverse opals is very complex and time-consuming by the processes described in the literature:

-   -   lengthy/complex production of the template or the arrangement of         the spheres forming the template-forming structure in spherical         closest packing     -   filling of the cavities of the template structure with         precursors, which is lengthy/complex since it frequently has to         be carried out a number of times     -   lengthy/complex procedure for removal of the templates     -   only limited or no possibility of the production of relatively         large photonic structures having an inverse opal structure and         scale-up of the laboratory synthesis into industrial production.

The disadvantages make the production of the desired photonic materials having an inverse opal structure more difficult. There is consequently a demand for a production process which is simple to implement and can also be scaled up to an industrial scale.

Core/shell particles whose shell forms a matrix and whose core is essentially solid and has an essentially monodisperse size distribution are described in German patent application DE-A-10145450. The use of core/shell particles whose shell forms a matrix and whose core is essentially solid and has an essentially monodisperse size distribution as templates for the production of inverse opal structures and a process for the production of inverse opal-like structures using core/shell particles of this type are described in the earlier German patent application DE 10245848.0. The mouldings described having homogeneous, regularly arranged cavities (i.e. inverse opal structure) preferably have walls of metal oxides or of elastomers. Consequently, the mouldings described are either hard and brittle or exhibit an elastomeric character with low mechanical loadability.

Surprisingly, it has now been found that the use of core/shell particles whose shell has thermoplastic properties results in mouldings having homogeneous, regularly arranged cavities whose mechanical properties are particularly advantageous.

The present invention therefore relates firstly to the use of core/shell particles whose shell forms a matrix and whose core is essentially solid and has an essentially monodisperse size distribution and whose shell is bonded to the core via an interlayer and whose shell has thermoplastic properties for the production of mouldings having homogeneous, regularly arranged cavities.

In the present invention, the term thermoplastic properties is taken to mean that the corresponding materials have a flow transition range above room temperature. In particular, this term is taken to mean materials which are termed thermoplastics in accordance with DIN 7724, Part 2, with the materials having energy-elastic behaviour at room temperature—i.e. the thermoplastics in the narrower sense—belonging to the preferred materials.

The present invention furthermore relates to a process for the production of mouldings having homogeneous, regularly arranged cavities, characterised in that core/shell particles whose shell forms a matrix and whose core is essentially solid and has an essentially monodisperse size distribution and is bonded to the core via an interlayer and whose shell has thermoplastic properties are converted into mouldings, preferably films, with application of mechanical force and elevated temperature, and the cores are subsequently removed.

The use according to the invention of core/shell particles results, in particular, in the following advantages:

-   -   on drying of the dispersions of core/shell particles, cracking         in the template (=arrangement of the spheres) during drying can         be reduced or even prevented entirely,     -   large-area regions of high order can be obtained in the         template,     -   stresses which arise during the drying process can be         compensated for by the elastic nature of the shell,     -   if polymers form the shell, these can intertwine with one         another and thus mechanically stabilise the regular sphere         arrangement in the template,     -   since the shell is strongly bonded to the core—preferably by         grafting—via an interlayer, the templates can be processed via         melt processes.

The present invention furthermore also relates to the products obtainable with the use according to the invention. Also claimed are therefore mouldings having homogeneous, regularly arranged cavities, characterised in that the regularly arranged cavities are embedded in a matrix having thermoplastic or thermosetting properties.

Owing to the easier processability, it is particularly preferred for the regularly arranged cavities to be embedded in a matrix having thermoplastic properties, where the matrix is preferably built up from poly(styrene), thermoplastic poly(acrylate) derivatives, preferably poly(methyl methacrylate) or poly(cyclohexyl methacrylate), or thermoplastic copolymers of these polymers with other acrylates, such as, preferably, styrene-acrylonitrile copolymers, styrene-ethyl acrylate copolymers or methyl methacrylate-ethyl acrylate copolymers.

For the purposes of the present invention, the term “built up” is taken to mean that the materials are present in such a large amount that the material properties of the mouldings are dominated by these polymers. However, the mouldings may also comprise other constituents, in particular processing aids, in amounts of up to 50% by weight.

In order to achieve the optical or photonic effect according to the invention, it is desirable for the core/shell particles to have a mean particle diameter in the range from about 5 nm to about 2000 nm. It may be particularly preferred here for the core/shell particles to have a mean particle diameter in the range from about 5 to 20 nm, preferably from 5 to 10 nm. In this case, the cores may be known as “quantum dots”; they exhibit the corresponding effects known from the literature. In order to achieve colour effects in the region of visible light, it is particularly advantageous for the core/shell particles to have a mean particle diameter in the region of about 50-800 nm. Particular preference is given to the use of particles in the range 100-600 nm and very particularly preferably in the range from 200 to 450 nm since in particles in this size range (depending on the refractive-index contrast which can be achieved in the photonic structure), the reflections of various wavelengths of visible light differ significantly from one another, and thus the opalescence which is particularly important for optical effects in the visible region occurs to a particularly pronounced extent in a very wide variety of colours. However, it is also preferred in a variant of the present invention to employ multiples of this preferred particle size, which then result in reflections corresponding to the higher orders and thus in a broad colour play.

The cavities of the mouldings according to the invention then in each case have corresponding mean diameters which are approximately identical to the diameters of the cores. The cavity diameter thus corresponds to about ⅔ of the core/shell particle diameter for preferred core/shell ratios of the particles. It is particularly preferred in accordance with the invention for the mean diameter of the cavities to be in the range about 50-500 nm, preferably in the range 100-500 nm and very particularly preferably in the range from 200 to 280 nm.

In a preferred embodiment of the invention, the interlayer is a layer of crosslinked or at least partially crosslinked polymers. The crosslinking of the interlayer here can take place via free radicals, for example induced by UV irradiation, or preferably via di- or oligofunctional monomers. Preferred interlayers in this embodiment comprise from 0.01 to 100% by weight, particularly preferably from 0.25 to 10% by weight, of di- or oligofunctional monomers. Preferred di- or oligofunctional monomers are, in particular, isoprene and allyl methacrylate (ALMA). Such an interlayer of crosslinked or at least partially crosslinked polymers preferably has a thickness in the range from 10 to 20 nm. If the interlayer comes out thicker, the refractive index of the layer is selected so that it corresponds either to the refractive index of the core or to the refractive index of the shell.

If copolymers which, as described above, contain a crosslinkable monomer are employed as interlayer, the person skilled in the art will have absolutely no problems in suitably selecting corresponding copolymerisable monomers. For example, corresponding copolymerisable monomers can be selected from a so-called Q-e-scheme (cf. textbooks on macromolecular chemistry). Thus, monomers such as methyl methacrylate and methyl acrylate can preferably be polymerised with ALMA.

In another, likewise preferred embodiment of the present invention, shell polymers are grafted directly onto the core via a corresponding functionalisation of the core. The surface functionalisation of the core here forms the interlayer according to the invention.

The type of surface functionalisation here depends principally on the material of the core. Silicon dioxide surfaces can, for example, advantageously be suitably modified with silanes carrying correspondingly reactive end groups, such as epoxy functions or free double bonds. The mono-disperse cores are dispersed in alcohols and modified with common organoalkoxysilanes. The silanisation of spherical oxide particles is also described in DE 43 16 814.

Silanisation of this type improves the dispersibility of inorganic cores and thus simplifies, in particular, the polymerisation-on of the interlayer polymers by emulsion polymerisation. Growing-on of the shell polymers can also be achieved directly via this functionalisation, i.e. the silane modification then serves as interlayer.

In a preferred embodiment, the shell of these core/shell particles consists of essentially uncrosslinked organic polymers, which are preferably grafted onto the core via an at least partially crosslinked interlayer. The core can consist of a very wide variety of materials. The only essential factor for the purposes of the present invention is that the cores can be removed under conditions under which the wall material is stable. The choice of suitable core/shell/interlayer/wall material combinations presents the person skilled in the art with absolutely no difficulties.

It is furthermore preferred in accordance with the invention for the core of the core/shell particles to consist of a material which is either not flowable or becomes flowable at a temperature above the melting point of the shell material. This can be achieved through the use of polymeric materials having a correspondingly high glass transition temperature (T_(g)), preferably crosslinked polymers, or through the use of inorganic core materials. The suitable materials are described below in detail.

It is furthermore particularly preferred in a variant of the invention for the cores to be built up from an inorganic material, preferably a metal or semimetal or a metal chalcogenide or metal pnictide. For the purposes of the present invention, the term chalcogenides is applied to compounds in which an element from group 16 of the Periodic Table is the electronegative bonding partner; the term pnictides is applied to those in which an element from group 15 of the Periodic Table is the electronegative bonding partner. Preferred cores consist of metal chalcogenides, preferably metal oxides, or metal pnictides, preferably nitrides or phosphides. For the purposes of these terms, the term metal is taken to mean all elements which can occur as electropositive partner compared with the counterions, such as the classical metals from the sub-groups, or the main-group metals from the first and second main groups, but equally well all elements from the third main group, as well as silicon, germanium, tin, lead, phosphorus, arsenic, antimony and bismuth. Preferred metal chalcogenides and metal pnictides include, in particular, silicon dioxide, aluminium oxide, gallium nitride, boron nitride, aluminium nitride, silicon nitride and phosphorus nitride.

In a variant of the present invention, the starting material employed for the production of the core/shell particles to be employed in accordance with the invention preferably comprises monodisperse cores of silicon dioxide, which can be obtained, for example, by the process described in U.S. Pat. No. 4,911,903. The cores here are produced by hydrolytic polycondensation of tetraalkoxysilanes in an aqueous/ammoniacal medium, where firstly a sol of primary particles is produced, and the resultant SiO₂ particles are subsequently converted to the desired particle size by continuous, controlled, metered addition of tetraalkoxysilane. This process enables the production of monodisperse SiO₂ cores having mean particle diameters of between 0.05 and 10 μm with a standard deviation of 5%.

Another starting material which can be employed comprises monodisperse cores of non-absorbent metal oxides, such as TiO₂, ZrO₂, ZnO₂, SnO₂ or Al₂O₃, or metal-oxide mixtures. Their production is described, for example, in EP 0 644 914. Furthermore, the process described in EP 0 216 278 for the production of monodisperse SiO₂ cores can be applied readily and with the same result to other oxides. Tetraethoxysilane, tetrabutoxytitanium, tetrapropoxyzirconium or mixtures thereof are added in one portion with vigorous mixing to a mixture of alcohol, water and ammonia, whose temperature is set precisely to from 30 to 40° C. by means of a thermostat, and the resultant mixture is stirred vigorously for a further 20 seconds, during which a suspension of monodisperse cores in the nanometre range forms. After a post-reaction time of from 1 to 2 hours, the cores are separated off in a conventional manner, for example by centrifugation, washed and dried.

In another preferred embodiment of the present invention, the core in the core/shell particles is essentially built up from a UV radiation-degradable material, preferably a UV-degradable organic polymer and particularly preferably of poly(tert-butyl methacrylate), poly(methyl methacrylate), poly(n-butyl methacrylate) or copolymers containing one of these polymers.

The wall of the moulding having homogeneous, regularly arranged cavities is formed from the polymers of the shell of the core/shell particles.

In the process according to the invention for the production of a moulding having homogeneous, regularly arranged cavities, a “positive” opal structure is formed as template in a first step through the application of a mechanical force to the core/shell particles.

For the purposes of the present invention, the action of mechanical force can be the action of a force which occurs in the conventional processing steps of polymers. In preferred variants of the present invention, the action of mechanical force takes place either:

-   -   through uniaxial pressing or     -   action of force during an injection-moulding operation or     -   during a transfer moulding operation,     -   during (co)extrusion or     -   during a calendering operation or     -   during a blowing operation.

If the action of force takes place through uniaxial pressing, the mouldings according to the invention are preferably films. Films according to the invention can preferably also be produced by calendering, film blowing or flat-film extrusion. The various ways of processing polymers under the action of mechanical forces are well known to the person skilled in the art and are revealed, for example, by the standard textbook Adolf Franck, “Kunststoff-Kompendium” [Plastics Compendium]; Vogel-Verlag; 1996. The processing of core/shell particles through the action of mechanical force, as is preferred here, is furthermore described in detail in international patent application WO 2003025035.

In a preferred variant of the production of mouldings according to the invention, the temperature during production is at least 40° C., preferably at least 60° C., above the glass transition temperature of the shell of the core/shell particles. It has been shown empirically that the flowability of the shell in this temperature range meets the requirements for economic production of the mouldings to a particular extent.

In a likewise preferred process variant which results in mouldings according to the invention, the flowable core/shell particles are cooled under the action of the mechanical force to a temperature at which the shell is no longer flowable.

If mouldings are produced by injection moulding, it is particularly preferred for the demoulding not to take place until after the mould with the moulding inside has cooled. When carried out in industry, it is advantageous to employ moulds having a large cooling-channel cross section since the cooling can then take place in a relatively short time. It has been found that cooling in the mould makes the colour effects according to the invention much more intense. It is assumed that better ordering of the core/shell particles to form the lattice occurs in this uniform cooling operation. It is particularly advantageous here for the mould to have been heated before the injection operation.

The mouldings according to the invention may, if it is technically advantageous, comprise auxiliaries and additives here. They can serve for optimum setting of the applicational data or properties desired or necessary for application and processing. Examples of auxiliaries and/or additives of this type are antioxidants, UV stabilisers, biocides, plasticisers, film-formation auxiliaries, flow-control agents, fillers, melting assistants, adhesives, release agents, application auxiliaries, demoulding auxiliaries, viscosity modifiers, for example thickeners.

Particularly recommended are additions of film-formation auxiliaries and film modifiers based on compounds of the general formula HO—C_(n)H_(2n)—O—(C_(n)H_(2n)—O)_(m)H, in which n is a number from 2 to 4, preferably 2 or 3, and m is a number from 0 to 500. The number n can vary within the chain, and the various chain members can be incorporated in a random or blockwise distribution. Examples of auxiliaries of this type are ethylene glycol, propylene glycol, di-, tri- and tetraethylene glycol, di-, tri- and tetrapropylene glycol, polyethylene oxides, polypropylene oxide and ethylene oxide-propylene oxide copolymers having molecular weights of up to about 15.000 and a random or block-like distribution of the ethylene oxide and propylene oxide units.

If desired, organic or inorganic solvents, dispersion media or diluents, which, for example, extend the open time of the formulation, i.e. the time available for its application to substrates, waxes or hot-melt adhesives are also possible as additives.

If desired, UV and weathering stabilisers can also be added to the mouldings. Suitable for this purpose are, for example, derivatives of 2,4-dihydroxybenzophenone, derivatives of 2-cyano-3,3′-diphenyl acrylate, derivatives of 2,2′,4,4′-tetrahydroxybenzophenone, derivatives of o-hydroxyphenylbenzotriazole, salicylic acid esters, o-hydroxyphenyl-s-triazines or sterically hindered amines. These substances may likewise be employed individually or in the form of a mixture.

The total amount of auxiliaries and/or additives is up to 40% by weight, preferably up to 20% by weight, particularly preferably up to 5% by weight, of the weight of the mouldings.

The cores can be removed by various methods. If the cores consist of suitable inorganic materials, they can be removed by etching. For example, silicon dioxide cores can preferably be removed using HF, in particular dilute HF solution. In this procedure, it may in turn be preferred for crosslinking of the shell to be carried out before or after removal of the cores, as described above. In this case, the shell and thus the matrix of the moulding attains thermosetting properties.

If the cores in the core/shell particles are built up from a UV-degradable material, preferably a UV-degradable organic polymer, the cores are removed by UV irradiation. In this procedure too, it may in turn be preferred for crosslinking of the shell to be carried out before or after removal of the cores, as described above.

If the cavities of the mouldings are to be re-impregnated with liquid or gaseous materials, however, it may also be preferred for the matrix to be crosslinked only to a very small extent, or not at all. The impregnation here can consist, for example, in inclusion of liquid crystals, as described, for example, in Ozaki et al., Adv. Mater. 2002, 14, 514 and Sato et al., J. Am. Chem. Soc. 2002, 124, 10950.

Through impregnation with these or other materials, the optical, electrical, acoustic and mechanical properties can be influenced by external energy fields. In particular, it is possible to use an external energy field to render these properties switchable in that removal of the field causes the system to exhibit different properties than in an applied field.

Locally addressable selection with the aid of the external field enables electro-optical devices to be produced in this way. The present invention therefore furthermore relates to the use of the mouldings according to the invention having homogeneous, regularly arranged cavities for the production of electro-optical devices and to electro-optical devices containing the mouldings according to the invention.

Electro-optical devices based on liquid crystals are extremely well known to the person skilled in the art and can be based on various effects. Examples of such devices are cells having dynamic scattering, DAP (deformation of aligned phases) cells, guest host cells, TN cells having a twisted nematic structure, STN (supertwisted nematic) cells, SBE (superbirefringence effect) cells and OMI (optical mode interference) cells. The commonest display devices are based on the Schadt-Helfrich effect and have a twisted nematic structure.

The corresponding liquid-crystal materials must have good chemical and thermal stability and good stability to electric fields and electromagnetic radiation. Furthermore, the liquid-crystal materials should have low viscosity and produce short addressing times, low threshold voltages and high contrast in the cells.

They should furthermore have a suitable mesophase, for example a nematic or cholesteric mesophase for the above-mentioned cells, at the usual operating temperatures, i.e. in the broadest possible range above and below room temperature. Since liquid crystals are generally used as mixtures of a plurality of components, it is important that the components are readily miscible with one another. Further properties, such as the electrical conductivity, the dielectric anisotropy and the optical anisotropy, have to satisfy various requirements depending on the cell type and area of application. For example, materials for cells having a twisted nematic structure should have positive dielectric anisotropy and low electrical conductivity.

For example, for matrix liquid-crystal displays with integrated non-linear elements for switching individual pixels (MLC displays), media having large positive dielectric anisotropy, relatively low birefringence, broad nematic phases, very high specific resistance, good UV and temperature stability and low vapour pressure are desired.

Matrix liquid-crystal displays of this type are known. Non-linear elements which can be used for individual switching-of the individual pixels are, for example, active elements (i.e. transistors). The term “active matrix” is then used, where a distinction can be made between two types:

1. MOS (metal oxide semiconductor) or other diodes on a silicon wafer as substrate.

2. Thin-film transistors (TFTs) on a glass plate as substrate.

The use of single-crystal silicon as substrate material restricts the display size, since even modular assembly of various part-displays results in problems at the joints.

In the case of the more promising type 2, which is preferred, the electro-optical effect used is usually the TN effect. A distinction is made between two technologies: TFTs comprising compound semiconductors, such as, for example, CdSe, or TFTs based on polycrystalline or amorphous silicon. Intensive work is being carried out worldwide on the latter technology.

The TFT matrix is applied to the inside of one glass plate of the display, while the other glass plate carries the transparent counterelectrode on its inside. Compared with the size of the pixel electrode, the TFT is very small and has virtually no adverse effect on the image. This technology can also be extended to fully colour-capable displays, in which a mosaic of red, green and blue filters is arranged in such a way that a filter element is opposite each switchable pixel.

The TFT displays usually operate as TN cells with crossed polarisers in transmission and are back-lit.

The term MLC displays here covers any matrix display with integrated non-linear elements, i.e., besides the active matrix, also displays with passive elements, such as varistors or diodes (MIM=metal-insulator-metal). MLC displays of this type are particularly suitable for TV applications (for example pocket TVs) or for high-information displays for computer applications (laptops) and in automobile or aircraft construction. With decreasing resistance, the contrast of an MLC display deteriorates, and the problem of after-image elimination may occur. Since the specific resistance of the liquid-crystal mixture generally drops over the life of an MLC display owing to interaction with the interior surfaces of the display, a high (initial) resistance is very important in order to achieve acceptable service lives. In the case of supertwisted (STN) cells, media are desired which enable greater multiplexability and/or lower threshold voltages and/or broader nematic phase ranges (in particular at low temperatures). To this end, a further widening of the available parameter latitude (clearing point, smectic-nematic transition or melting point, viscosity, dielectric parameters, elastic parameters) is urgently desired.

The mouldings according to the invention can in principle, on combination with liquid-crystal mixtures suitable in each case which are known to the person skilled in the art, be employed in electro-optical displays based on all principles described, in particular for MLC, IPS, TN or STN displays.

The mouldings having homogeneous, regularly arranged cavities obtainable in accordance with the invention are suitable firstly for the above-described use as photonic material, preferably with the impregnation mentioned, but secondly also for the production of porous surfaces, membranes, separators, filters and porous supports. These materials can also be used, for example, as fluidised beds in fluidised-bed reactors.

Owing to the considerations mentioned here, it is advantageous for the shell of the core/shell particles according to the invention to comprise one or more polymers and/or copolymers or polymer precursors and, if desired, auxiliaries and additives, where the composition of the shell may be selected in such a way that it is essentially dimensionally stable and tack-free in a non-swelling environment at room temperature.

With the use of polymer substances as shell material and, if desired, core material, the person skilled in the art gains the freedom to determine their relevant properties, such as, for example, their composition, the particle size, the mechanical data, the glass transition temperature, the melting point and the core:shell weight ratio and thus also the applicational properties of the core/shell particles, which ultimately also affect the properties of the mouldings produced therefrom.

In principle, all polymers of the classes already mentioned above, if they are selected or constructed in such a way that they conform to the specification given above for the shell polymers, are suitable for the shell material.

Polymers which meet the specifications for a shell material are likewise present in the groups of polymers and copolymers of polymerisable unsaturated monomers and polycondensates and copolycondensates of monomers containing at least two reactive groups, such as, for example, high-molecular-weight aliphatic, aliphatic/aromatic or fully aromatic polyesters and polyamides.

Taking into account the above conditions for the properties of the shell polymers (=matrix polymers), selected units from all groups of organic film formers are in principle suitable for their preparation.

Some further examples are intended to illustrate the broad range of polymers which are suitable for the production of the shells.

If the shell is intended to have a comparatively low refractive index, polymers such as polyacrylates, polymethacrylates, polybutadiene, polymethyl. methacrylate, polyesters, polyamides and polyacrylonitrile,. for example, are suitable.

If the shell is intended to have a comparatively high refractive index, polymers having a preferably aromatic basic structure, such as polystyrene, polystyrene copolymers, such as, for example, SAN, aromatic-aliphatic polyesters and polyamides, aromatic polysulfones and polyketones, and, on suitable selection of a high-refractive-index core material, also polyacrylonitrile, for example, are suitable for the shell.

With respect to the processability of the core/shell particles into inverse opal structures, it is preferred for the core:shell weight ratio to be in the range from 5:1 to 1:10, in particular in the range from 2:1 to 1:5 and particularly preferably in the range from 1.5:1 to 1:2.

The core/shell particles which can be used in accordance with the invention can be produced by various processes.

A preferred way of obtaining the particles is a process for the production of core/shell particles by a) surface treatment of monodisperse cores, and b) application of the shell of organic polymers to the treated cores.

In a preferred process variant, a crosslinked polymeric interlayer, which preferably contains reactive centres to which the shell can be covalently bonded, is applied to the cores, preferably by emulsion polymerisation or by ATR polymerisation. ATR polymerisation here stands for atom transfer radical polymerisation, as described, for example, in K. Matyjaszewski, Practical Atom Transfer Radical Polymerisation, Polym. Mater. Sci. Eng. 2001, 84. The encapsulation of inorganic materials by means of ATRP is described, for example, in T. Werne, T. E. Patten, Atom Transfer Radical Polymerisation from Nanoparticles: A Tool for the Preparation of Well-Defined Hybrid Nanostructures and for, Understanding the Chemistry of Controlled/“Living” Radical Polymerisation from Surfaces, J. Am. Chem. Soc. 2001, 123, 7497-7505 and WO 00/11043. The performance both of this method and of emulsion polymerisations is familiar to the person skilled in the art of polymer preparation and is described, for example, in the above-mentioned literature references.

The liquid reaction medium in which the polymerisations or copolymerisations can be carried out consists of the solvents, dispersion media or diluents usually employed in polymerisations, in particular in emulsion polymerisation processes. The choice here is made in such a way that the emulsifiers employed for homogenisation of the core particles and shell precursors are able to develop adequate efficacy. Suitable liquid reaction media for carrying out the process according to the invention are aqueous media, in particular water.

Suitable for initiation of the polymerisation are, for example, polymerisation initiators which decompose either thermally or photochemically, form free radicals and thus initiate the polymerisation. Preferred thermally activatable polymerisation initiators here are those which decompose at between 20 and 180° C., in particular at between 20 and 80° C. Particularly preferred polymerisation initiators are peroxides, such as dibenzbyl peroxide, di-tert-butyl peroxide, peresters, percarbonates, perketals, hydroperoxides, but also inorganic peroxides, such as H₂O₂, salts of peroxosulfuric acid and peroxodisulfuric acid, azo compounds, alkylboron compounds, and hydrocarbons which decompose homolytically. The initiators and/or photoinitiators, which, depending on the requirements of the polymerised material, are employed in amounts of between 0.01 and 15% by weight, based on the polymerisable components, can be used individually or, in order to utilise advantageous synergistic effects, in combination with one another. In addition, use is made of redox systems, such as, for example, salts of peroxodisulfuric acid and peroxosulfuric acid in combination with low-valency sulfur compounds, particularly ammonium peroxodisulfate in combination with sodium dithionite.

Corresponding processes have also been described for the production of polycondensation products. Thus, it is possible for the starting materials for the production of polycondensation products to be dispersed in inert liquids and condensed, preferably with removal of low-molecular-weight reaction products, such as water or—for example on use of di(lower alkyl) dicarboxylates for the preparation of polyesters or polyamides—lower alkanols.

Polyaddition products are obtained analogously by reaction of compounds which contain at least two, preferably three, reactive groups, such as, for example, epoxide, cyanate, isocyanate or isothiocyanate groups, with compounds carrying complementary reactive groups. Thus, isocyanates react, for example, with alcohols to give urethanes and with amines to give urea derivatives, while epoxides react with these complementary groups to give hydroxyethers and hydroxyamines respectively. Like the polycondensations, polyaddition reactions can also advantageously be carried out in an inert solvent or dispersion medium.

The stable dispersions required for these polymerisation, polycondensation or polyaddition processes are generally prepared using dispersion auxiliaries.

The dispersion auxiliaries used are preferably water-soluble, high-molecular-weight organic compounds containing polar groups, such as polyvinylpyrrolidone, copolymers of vinyl propionate or acetate and vinylpyrrolidone, partially saponified copolymers of an acrylate and acrylonitrile, polyvinyl alcohols having different residual acetate contents, cellulose ethers, gelatin, block copolymers, modified starch, low-molecular-weight polymers containing carboxyl and/or sulfonyl groups, or mixtures of these substances.

Particularly preferred protective colloids are polyvinyl alcohols having a residual acetate content of less than 35 mol %, in particular from 5 to 39 mol %, and/or vinylpyrrolidone-vinyl propionate copolymers having a vinyl ester content of less than 35% by weight, in particular from 5 to 30% by weight.

It is possible to use nonionic or ionic emulsifiers, if desired also as a mixture. Preferred emulsifiers are optionally ethoxylated or propoxylated, relatively long-chain alkanols or alkylphenols having different degrees of ethoxylation or propoxylation (for example adducts with from 0 to 50 mol of alkylene oxide) or neutralised, sulfated, sulfonated or phosphated derivatives thereof. Neutralised dialkylsulfosuccinic acid esters or alkyldiphenyl oxide disulfonates are also particularly suitable.

Particularly advantageous are combinations of these emulsifiers with the above-mentioned protective colloids, since particularly finely divided dispersions are obtained therewith.

Through the setting of the reaction conditions, such as temperature, pressure, reaction duration and use of suitable catalyst systems, which influence the degree of polymerisation in a known manner, and the choice of the monomers employed for their production—in terms of type and proportion—the desired property combinations of the requisite polymers can be set specifically. The particle size here can be set, for example, through the choice and amount of the initiators and other parameters, such as the reaction temperature. The corresponding setting of these parameters presents the person skilled in the art in the area of polymerisation with absolutely no difficulties.

Monomers which result in polymers having a high refractive index are generally those which contain aromatic moieties or those which contain hetero atoms having a high atomic number, such as, for example, those halogen atoms, in particular bromine or iodine atoms, sulfur or metal ions, i.e. atoms or atomic groups which increase the polarisability of the polymers.

Polymers having a low refractive index are accordingly obtained from monomers or monomer mixtures which do not contain the said moieties and/or atoms of high atomic number or only do so in a small proportion.

A review of the refractive indices of various common homopolymers is given, for example, in Ullmanns Encyklopädie der technischen Chemie [Ullmann's Encyclopaedia of Industrial Chemistry], 5th Edition, Volume A21, page 169. Examples of monomers which can be polymerised by means of free radicals and result in polymers having a high refractive index are:

Group a): styrene, styrenes which are alkyl-substituted on the phenyl ring, α-methylstyrene, mono- and dichlorostyrene, vinylnaphthalene, isopropenylnaphthalene, isopropenylbiphenyl, vinylpyridine, isopropenylpyridine, vinylcarbazole, vinylanthracene, N-benzylmethacrylamide and p-hydroxymethacrylanilide.

Group b): acrylates containing aromatic side chains, such as, for example, phenyl (meth)acrylate (=abbreviated notation for the two compounds phenyl acrylate and phenyl methacrylate) and benzyl (meth)acrylate. Group c): an increase in the refractive index of the polymers is also achieved by copolymerisation of carboxyl-containing monomers and conversion of the resultant “acidic” polymers into the corresponding salts with metals of relatively high atomic weight, such as, for example, preferably with K, Ca, Sr, Ba, Zn, Pb, Fe, Ni, Co, Cr, Cu, Mn, Sn or Cd.

The above-mentioned monomers, which make a considerable contribution towards the refractive index of the polymers produced therefrom, can be homopolymerised or copolymerised with one another. They can also be copolymerised with a certain proportion of monomers which make a lesser contribution towards the refractive index. Such copolymerisable monomers having a lower refractive index contribution are, for example, acrylates, methacrylates, vinyl ethers or vinyl esters containing purely aliphatic radicals.

In addition, crosslinking agents which can be employed for the production of crosslinked matrix materials from polymers produced by means of free radicals are also all bifunctional or polyfunctional compounds which are copolymerisable with the above-mentioned monomers or which can subsequently react with the polymers with crosslinking.

Examples of suitable crosslinking agents are presented below, divided into groups for systematisation:

Group 1: bisacrylates, bismethacrylates and bisvinyl ethers of aromatic or aliphatic di- or polyhydroxyl compounds, in particular of butanediol (butanediol di(meth)acrylate, butanediol bisvinyl ether), hexanediol (hexanediol di(meth)acrylate, hexanediol bisvinyl ether), pentaerythritol, hydroquinone, bishydroxyphenylmethane, bishydroxyphenyl ether, bishydroxymethylbenzene, bisphenol A or with ethylene oxide spacers, propylene oxide spacers or mixed ethylene oxide/propylene oxide spacers.

Further crosslinking agents from this group are, for example, di- or polyvinyl compounds, such as divinylbenzene, or methylenebisacrylamide, triallyl cyanurate, divinylethyleneurea, trimethylolpropane tri(meth)acrylate, trimethylolpropane trivinyl ether, pentaerythritol tetra(meth)acrylate, pentaerythritol tetravinyl ether, and crosslinking agents having two or more different reactive ends, such as, for example, (meth)allyl (meth)acrylates of the formulae:

(in which R is hydrogen or methyl).

Group 2: reactive crosslinking agents which act in a crosslinking manner, but in most cases in a post-crosslinking manner, for example during warming or drying, and which are copolymerised into the core or shell polymers as copolymers.

Examples thereof are: N-methylol(meth)acrylamide, acrylamidoglycolic acid, and ethers and/or esters thereof with C₁- to C₆-alcohols, diacetoneacrylamide (DAAM), glycidyl methacrylate (GMA), methacryloyloxypropyltrimethoxysilane (MEMO), vinyltrimethoxysilane and m-isopropenylbenzyl isocyanate (TMI).

Group 3: carboxyl groups which have been incorporated into the polymer by copolymerisation of unsaturated carboxylic acids are crosslinked in a bridge-like manner via polyvalent metal ions. The unsaturated carboxylic acids employed for this purpose are preferably acrylic acid, methacrylic acid, maleic anhydride, itaconic acid and fumaric acid. Suitable metal ions are Mg, Ca, Sr, Ba, Zn, Pb, Fe, Ni, Co, Cr, Cu, Mn, Sn and Cd. Particular preference is given to Ca, Mg and Zn, Ti and Zr. In addition, monovalent metal ions, such as, for example, Na or K, are also suitable.

Group 4: post-crosslinked additives, which are taken to mean bis- or polyfunctionalised additives which react irreversibly with the polymer (by addition or preferably condensation reactions) with formation of a network. Examples thereof are compounds which contain at least two of the following reactive groups per molecule: epoxide, aziridine, isocyanate, acid chloride, carbodiimide or carbonyl groups, furthermore, for example, 3,4-dihydroxyimidazolinone and derivatives thereof.

As already explained above, post-crosslinking agents containing reactive groups, such as, for example, epoxide and isocyanate groups, require complementary reactive groups in the polymer to be crosslinked. Thus, isocyanates react, for example, with alcohols to give urethanes, with amines to give urea derivatives, while epoxides react with these complementary groups to give hydroxyethers and hydroxyamines respectively.

The term post-crosslinking is also taken to mean photochemical curing or oxidative or air- or moisture-induced curing of the systems.

The above-mentioned monomers and crosslinking agents can be combined and (co)polymerised with one another as desired and in a targeted manner in such a way that an optionally crosslinked (co)polymer having the desired refractive index and the requisite stability criteria and mechanical properties is obtained.

It is also possible additionally to copolymerise further common monomers, for example acrylates, methacrylates, vinyl esters, butadiene, ethylene or styrene, in order, for example, to set the glass transition temperature or the mechanical properties of the shell polymers as needed.

It is likewise preferred in accordance with the invention for the application of the shell of organic polymers to be carried out by grafting, preferably by emulsion polymerisation or ATR polymerisation. The methods and monomers described above can be employed correspondingly here.

The following examples are intended to explain the invention in greater detail without limiting it.

EXAMPLES

Abbreviations:

-   ALMA allyl methacrylate -   CHMA cyclohexyl methacrylate -   KOH potassium hydroxide -   SDS sodium dodecylsulfate -   MMA methyl methacrylate -   MPS methacryloxypropyltrimethoxysilane -   PCHMA poly(cyclohexyl methacrylate) -   PMMA poly(methyl methacrylate) -   PS polystyrene -   PTBMA poly(tert-butyl methacrylate) -   SPS sodium peroxodisulfate -   TEOS tetraethyl orthosilicate -   TBMA tert-butyl methacrylate     Monomers and Chemicals:

KOH, SPS, SDS, TEOS, sodium bisulfite, sodium peroxodisulfate, ammonia solution 25% (all VWR), Triton X405 (Fluka) and MPS (Dynasilan™ MEMO, Degussa) are used as obtained. ALMA (Degussa) is destabilised using Dehibit™ 100 (Polyscience). Styrene (BASF) and CHMA (Degussa) are distilled under reduced pressure. MMA (BASF) was washed by shaking with 1N sodium hydroxide solution, washed with water until neutral and dried over sodium sulfate. The water content of the technical-grade absolute ethanol (Mundo) is determined by Karl Fischer titration as 0.14% by weight.

Example 1

Production of SiO₂ Cores

The SiO₂ cores are produced by hydrolysis and condensation of TEOS in a solution of water, ammonia and ethanol by a modified Stöber process. Firstly, seed particles are produced and subsequently enlarged in a step process. In order to synthesise the seed particles, 500 ml of ethanol and 25 ml of ammonia solution (25% by weight) are initially introduced into a 2 l round-bottomed flask with water bath, magnetic stirrer and pressure equalisation. When the reaction temperature of 35° C. has been reached, 19 ml of TEOS are injected rapidly. After stirring for 2.5 hours, the particles are enlarged by addition of 4 ml of ammonia solution and injection of 15 ml of TEOS. In order to complete the reaction, the mixture is stirred for a further 4 hours. The suspension formed comprises 0.69M NH₃, 2M H₂O and 2.5% by weight of SiO₂.

The seed particles are enlarged stepwise. To this end, the suspension is diluted with ethanol and ammonia solution in such a way that the concentration of SiO₂ is 0.5% by weight before each reaction step and 2.5% by weight after the reaction step. The concentrations of ammonia and water are kept constant at 0.69M NH₃ and 2M H₂O. For example, 265 ml of SiO₂ suspension are initially introduced into a 2 l round-bottomed flask with water bath, magnetic stirrer and pressure equalisation and diluted with 165.5 ml of ethanol and 9.5 ml of ammonia solution (25% by weight). When the reaction temperature of 35° C. has been reached, 13 ml of TEOS are injected rapidly. In order to complete the reaction, the mixture is stirred for at least 4 hours. The next reaction step can be carried out directly thereafter or after cooling and storage of the suspension for a number of days.

Analysis of the particle diameters by TEM gives the following correlations: Dry colour Mean diameter Standard deviation pale violet 143 nm 5.6% violet 184 nm 4.9% blue-green 218 nm 4.2% yellow-green 270 nm   4%

Example 2

Functionalisation of the SiO₂ Cores

3 ml of MPS dissolved in ethanol are added with stirring at room temperature to 1.3 l of ethanolic suspension comprising 2.5% by weight of SiO₂ (SiO₂ suspension having a violet dry colour (wavelength maximum l 111=400 nm, mean particle diameter according to TEM 201 nm; according to Example 1), 0.69M NH₃ and 2M H₂O. The mixture is firstly warmed slowly to 65° C. under atmospheric pressure in a rotary evaporator. After 1.5 hours, distillation of an azeotropic mixture of ethanol and water is commenced by reducing the pressure. The liquid distilled off is replaced with absolute ethanol. In total, 1.2 l of ethanol/water mixture are removed. After 2 hours, the reaction solution is concentrated to 300 ml and transferred into a 1 l round-bottomed flask. 0.06 g of SDS, dissolved in 120 g of water, is added, and ethanol is again distilled off at 65° C. The liquid distilled off is replaced with water.

The other samples from Example 1 are reacted analogously.

Example 3

Emulsion Polymerisation

The emulsion polymerisation is carried out in a double-walled, 250 ml glass reactor thermostatted at 75° C. and fitted with inert-gas inlet, propeller stirrer and reflux condenser. Argon is bubbled through 110 g (comprising 17 g of SiO₂) of SiO₂ suspension as described in Example 2 for 20 minutes. 0.1 g of SDS is then added, and the mixture is introduced into the reactor. 0.05 g of SPS, dissolved in 3 g of water, is subsequently added. After 15 minutes, a monomer emulsion comprising 5.4 g of MMA, 0.6 g of ALMA, 0.02 g of SDS (0.33% by weight, based on the monomer), 0.04 g of KOH and 30 g of water is metered in continuously over a period of 90 minutes. The reactor contents are stirred for 20 minutes without further addition. 0.02 g of APS, dissolved in 3 g of water, is then added. After 10 minutes, a second monomer emulsion comprising 20 g of CHMA, 0.08 g of SDS (0.4% by weight, based on the monomer) and 40 g of water is metered in continuously over a period of 200 minutes. In order to virtually complete the reaction of the monomers, the mixture is subsequently stirred for a further 120 minutes. The core/shell particles are subsequently precipitated in 500 ml of ethanol, the precipitation is completed by addition of 15 g of concentrated aqueous sodium chloride solution, 500 ml of distilled water are added to the suspension, the mixture is filtered through a suction filter, and the polymer is dried at 50° C. under reduced pressure.

Example 4

Production of the Template Film

The dried, pulverulent polymers from Example 3 are granulated at 200° C. in an extruder (DSM Research microextruder). The granules are heated in a hydraulic press (Collin 300 P) and pressed at a pre-specified hydraulic pressure. The mould used comprises flat, PET film-covered metal plates. A typical pressing programme for the production of films having a diameter of about 10 cm and a thickness of about 0.15 mm is:

-   initial weight 2-3 g of polymer; -   preheating for 5 minutes at 180° C., without pressure; -   pressing for 3 minutes at a hydraulic pressure of 1 bar at 180° C.; -   pressing for 3 minutes at a hydraulic pressure of 150 bar at 180°     C.; slow cooling for 10 minutes at a hydraulic pressure of 150 bar,     reaching about 90° C.; -   rapid cooling to room temperature, without pressure.

Example 5

Etching of the Films using Hydrofluoric Acid

The films are covered with hydrofluoric acid (10% by weight) in open vessels and treated at RT for one week. Evaporating hydrofluoric acid is replaced with fresh. After rinsing with water and drying, the etched film pieces exhibit clearly evident reflection colours.

Investigation of ultrathin sections (100 nm) of the films after etching confirms that the SiO₂ cores are dissolved out of the films with retention of the ordering and films with ordered porosity are formed (FIGS. 1 and 2). Throughout the cross section of the film, pores are formed by dissolution of SiO₂ cores, with virtually all SiO₂ cores being removed in a range from the surface of the film down to a depth of about 5 μm.

Example 6

Production of a Latex PTBMAcsPS

50 mg of sodium bisulfite, dissolved in 5 g of water, are admixed with an emulsion, thermostatted at 4° C., consisting of 217 g of water, 0.4 g of ALMA, 3.6 g of TBMA and 30 mg of SDS, and the emulsion is transferred into the reactor pre-heated to 75° C. Immediately after introduction, the reaction is initiated by addition of 220 mg of sodium peroxodisulfate and a further 50 mg of sodium bisulfite, in each case dissolved in 5 g of water. After 20 minutes, monomer emulsion I comprising 9.6 g of ALMA, 96 g of TBMA, 0.45 g of SDS, 0.1 g of KOH and 130 g of water is metered in continuously over a period of 180 minutes. The reactor contents are stirred for 30 minutes without further addition. 150 mg of sodium peroxodisulfate, dissolved in 5 g of water, are then added. After stirring for 15 minutes, monomer emulsion II comprising 120 g of styrene, 0.4 g of SDS and 120 g of water is metered in continuously over a period of 200 minutes. In order to virtually complete the reaction of the monomers, the mixture is subsequently stirred for a further 60 minutes. Dried samples of the latex exhibit a green colour. Investigation of precipitates of the latex by electron microscopy shows that the polymer particles have an irregular shape and an average particle size of about 210 nm. The core/shell particles are subsequently precipitated in 1 litre of ethanol, the precipitation is completed by addition of 25 g of concentrated aqueous sodium chloride solution, 1 litre of distilled water is added to the suspension, the mixture is filtered through a suction filter, and the polymer is dried at 50° C. under reduced pressure.

Further latices having a larger particle diameter and more uniform particle shape are produced by changing the emulsifier type and concentration: Example 6a 6b 6c 6d Initial mixture Water 217 g 217 g 217 g 217 g ALMA 0.4 g 0.4 g 0.4 g 0.4 g TBMA 3.6 g 3.6 g 3.6 g 3.6 g SDS 0.03 g 0.03 g 0.03 g 0.03 g Initiation Sodium 0.05 g 0.05 g 0.05 g 0.05 g bisulfite Sodium 0.22 g 0.2 g 0.2 g 0.2 g peroxodi- sulfate Sodium 0.05 g 0.05 g 0.05 g 0.05 g bisulfite Emulsion I Water 130 g 130 g 130 g 130 g TBMA 96 g 96 g 96 g 96 g ALMA 9.6 g 9.6 g 9.6 g 9.6 g SDS 0.45 g 0.4 g 0.4 g 0.4 g Triton X 405 0.2 g 0.2 g 0.2 g KOH 0.1 g 0.1 g 0.1 g 0.1 g Initiator Sodium 0.15 g 0.1 g 0.1 g 0.1 g peroxodi- sulfate Emulsion II Water 120 g 140 g 140 g 140 g Styrene 120 g 120 g 120 g 120 g SDS 0.4 g 0.4 g 0.4 g 0.4 g Triton X405 0.3 g 0.3 g 0.3 g Colour green red (secondary green (secondary reddish planes) planes)

Example 7

Pressing of the Films

In order to produce films, the polymer powders from Examples 6a-6d are heated in a hydraulic press (Collin 300 P), and the melt is pressed at a pre-specified hydraulic pressure. The mould used comprises flat, PEt film-covered metal plates. A typical pressing programme for the production of films having a diameter of about 10 cm and a thickness of about 0.2 mm is:

-   initial weight 1-2 g of polymer; -   preheating for 5 minutes at 1 80° C., without pressure; -   pressing for 3 minutes at a hydraulic pressure of 1 bar at 180° C.; -   pressing for 3 minutes at a hydraulic pressure of 150 bar at 180°     C.; -   slow cooling for 10 minutes at a hydraulic pressure of 150 bar,     reaching about 90° C.; -   rapid cooling to room temperature, without pressure.

Example 8

Production of Mouldings having Homogeneous, Regularly Arranged Cavities

The films from Example 7 are laid beneath a UV lamp (high-pressure HG vapour lamp, power 300 watts, lamp-film distance: 20 cm) over a period of 24 hours. After the UV exposure, the films exhibit bright, iridescent colour effects. FIG. 8 shows the cavities of the moulding obtained as described in Examples 6a, 7 and 8.

KEY TO FIGURES

FIGS. 1 a and 1 b: Transmission electron photomicrograph (TEM photograph) of ultrathin sections (100 nm) of the cross section of etched films from Example 5. A film cross section is shown. The epoxy resin used for embedding the films can be seen at bottom right of the figures. The arrangement of the pores (pale) in the polymer matrix (dark) starting from the film surface can be seen.

FIG. 2: Scanning electron photomicrograph (SEM photograph) of the surface of an HF-etched film from Example 5. Regularly arranged pores formed by dissolution of the SiO₂ cores are evident at the damaged point.

FIG. 3: Scanning electron photomicrograph (SEM photograph) of the surface of a UV light-treated film from Example 8. 

1. Use of core/shell particles whose shell forms a matrix and whose core is essentially solid and has an essentially monodisperse size distribution and whose shell is bonded to the core via an interlayer and whose shell has thermoplastic properties for the production of mouldings having homogeneous, regularly arranged cavities.
 2. Use according to claim 1, characterised in that the core consists of a material which is either not flowable or becomes flowable at a temperature above the melting point of the shell material.
 3. Use according to claim 1, characterised in that the core:shell weight ratio in the core/shell particles is in the range from 5:1 to 1:10, in particular in the range from 2:1 to 1:5 and particularly preferably in the range from 1.5:1 to 1:2.
 4. Use according to claim 1, characterised in that the shell in the core/shell particles consists of essentially uncrosslinked organic polymers which are grafted onto the core via an at least partially crosslinked interlayer, where the shell preferably comprises poly(styrene), thermoplastic poly(acrylate) derivatives, particularly preferably poly(methyl methacrylate) or poly(cyclohexyl methacrylate), or thermoplastic copolymers of these polymers with other acrylates, such as, preferably, styrene-acrylonitrile copolymers, styrene-ethyl acrylate copolymers or methyl methacrylate-ethyl acrylate copolymers, and the interlayer is preferably built up from methyl methacrylate-allyl methacrylate copolymers.
 5. Use according to claim 1, characterised in that the core in the core/shell particles is essentially built up from an inorganic material, preferably a metal or semimetal or a metal chalcogenide or metal pnictide, particularly preferably silicon dioxide.
 6. Use according to claim 1, characterised in that the core in the core/shell particles is essentially built up from a UV-degradable material, preferably a UV-degradable organic polymer and particularly preferably from poly(tert-butyl methacrylate), poly(methyl methacrylate), poly(n-butyl methacrylate) or copolymers containing one of these polymers.
 7. Use according to claim 1, characterised in that the core/shell particles have a mean particle diameter in the range about 50-800 nm, preferably in the range from 100-600 nm and particularly preferably in the range from 200 to 450 nm.
 8. Use according to claim 1, characterised in that the cores have a surface modification, preferably with silanes carrying reactive end groups, such as epoxide functions or free double bonds.
 9. Use according to claim 1, characterised in that the mouldings are films.
 10. Process for the production of mouldings having homogeneous, regularly arranged cavities, characterised in that core/shell particles whose shell forms a matrix and whose core is essentially solid and has an essentially monodisperse size distribution and is bonded to the core via an interlayer and whose shell has thermoplastic properties are converted into mouldings, preferably films, with application of a mechanical force and elevated temperature, and the cores are subsequently removed.
 11. Process according to claim 10, characterised in that a mechanical force is applied through uniaxial pressing or during an injection-moulding operation or during a transfer-moulding operation or during (co)extrusion or during a calendering operation or during a blowing operation.
 12. Process according to claim 10, characterised in that the core/shell particles are cooled under the action of the mechanical force to a temperature at which the shell is no longer flowable.
 13. Process according to claim 10, characterised in that the cores are removed by etching, preferably by etching using HF.
 14. Process according to claim 10, characterised in that the cores are removed by UV irradiation.
 15. Process according to claim 10, characterised in that crosslinking of the shell is carried out before or after removal of the cores.
 16. Mouldings having homogeneous, regularly arranged cavities, characterised in that the regularly arranged cavities are embedded in a matrix having thermoplastic or thermosetting properties.
 17. Mouldings according to claim 16, characterised in that the regularly arranged cavities are embedded in a matrix having thermoplastic properties.
 18. Mouldings according to claim 16, characterised in that the matrix is built up from poly(styrene), thermoplastic poly(acrylate) derivatives, preferably poly(methyl methacrylate) or poly(cyclohexyl methacrylate), or thermoplastic copolymers of these polymers with other acrylates, such as, preferably, styrene-acrylonitrile copolymers, styrene-ethyl acrylate copolymers or methyl methacrylateethyl acrylate copolymers.
 19. Mouldings according to claim 16, characterised in that the cavities have a mean diameter in the range about 50-500 nm, preferably in the range from 100-500 nm and very particularly preferably in the range from 200 to 280 nm.
 20. Use of mouldings according to claim 16 as photonic material.
 21. Use of mouldings according to claim 16 for the production of electro-optical devices.
 22. Electro-optical device containing mouldings according to claim
 16. 